Age-Hardening Process Featuring Anomalous Aging Time

ABSTRACT

This document describes a process/strategy for age hardening nickel based alloys to create desirable properties with reduced energy expenditure. The inventive process introduces isolated atom nucleation sites to accelerate the nucleation rate by approximately 36 times, thereby permitting age hardening to occur in significantly less time and with significantly less energy expenditure.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was developed at the National High Magnetic Field Laboratory in Tallahassee, Fla. The research has been funded in part by National Science Foundation Contract No. DMR-0654118.

This is a non-provisional patent application filed pursuant to the provisions of 37 C.F.R. §1.53(c).

CROSS-REFERENCES TO RELATED APPLICATIONS

Not applicable.

MICROFICHE APPENDIX

Not Applicable

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of metallurgy. More specifically, the invention comprises a method for achieving accelerated age hardening in superalloys made of nickel, chromium, and molybdenum by the addition of rhenium.

2. Description of the Related Art

Age hardening (also known as “precipitation hardening”) is used to produce various alloys with desirable properties. The process is used to mechanically strengthen malleable materials for structural applications. In addition to steels, precipitation hardening is commonly used for aluminum, titanium, and nickel alloys. The process produces fine particles of impurity phases, which act as barriers to the motion of crystallographic lattice dislocations.

Precipitation in solids can produce many different sizes of particles, which have radically different strengthening effects as demonstrated by the following equation:

Δσ=2/(πE)^(−1/2)(λ_(apb) /b)^(3/2) r ^(1/2) f ^(1/2)

where E is the Young's modulus, λ_(apb) is the anti-phase interfacial energy, b is the Burger's vector, r is the size of the precipitates, and f is the volume fraction. Both r and f can be related to l, the distance between the precipitates. If the volume fraction is held constant, then one observes an optimized value for the size of the precipitates (r) at which the material reaches a maximum strength.

The optimal size of the precipitates formed depends upon the thermo-mechanical history of the alloy being hardened. In the prior art, alloys must be kept at elevated temperature for several hours to allow precipitation to take place. Thus, conventional precipitation hardening requires a substantial amount of energy (The large amount of time required is why the process is also referred to as “age hardening”).

On the other hand, if the process and alloys are altered so that the precipitates can form in a relatively short period of time, the temporal window for achieving an optimal result usually becomes very narrow. It is then easy to “over-age” the alloy. When a material is over-aged (held at the elevated temperature for too long), then both the size of the precipitates and the distance between the precipitates become too large and the Orowan process operates. At certain values for l and for r, the strength or hardness drops significantly to a value governed by a rule-of-mixture.

Another known technique to accelerate the formation of precipitates is to deform the materials in order to increase the dislocation densities (which enhances the diffusion along the dislocation). Unfortunately, deformation processes are also energy-intensive and therefore expensive.

Accordingly, it is desirable to provide a precipitation hardening process which can be completed more rapidly than the known prior art, which has a relatively broad time window for optimal results, and which does not require the use of mechanical deformation.

BRIEF SUMMARY OF THE INVENTION

The present invention comprises a process or strategy for age hardening nickel based alloys to create desirable properties. The inventive process introduces isolated atom nucleation sites to accelerate the nucleation rate by approximately 36 times, thereby permitting age hardening to occur in significantly less time and with significantly less energy expenditure.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a plot of hardness versus aging time at a temperature of 873 K.

FIG. 2 is a plot of hardness versus aging time at a temperature of 923 K, comparing one of the inventive alloys to a prior art alloy.

FIG. 3 is a plot of hardness versus aging time for three alloys made according to the present inventive process. The three alloys were deformed to different strain (41%, 62%, and 69%) before the aging.

DETAILED DESCRIPTION OF THE INVENTION

The present invention uses alloys made of Cr—Ni—Mo—Re, which are formulated to allow a very different age hardening process from the prior art alloys. The alloys thus formulated can be age hardened in as little as 5 minutes. The same alloy shows stable mechanical properties without over-aging even after a prolonged aging period (up to 500 hours). Thus, the “window” of optimal time for age hardening is quite broad.

The new allow was based on a Ni—Mo—Cr alloy, to which rhenium was added. The Ni—Mo—Cr alloy has a face centered cubic structure above about 1123 K with short-range-ordered (SRO) domains. A long-range-ordered (LRO) domains form below 1123 K. The alloys are strengthened mainly by formation of LRO precipitates. In order to accelerate the age hardening, cold deformation is introduced before the hardening. When a sample of Ni—Mo—Cr is 40% cold worked and then heated to 923 K, 2 hours of hardening time is required to provide a strength equivalent to prior art samples aged to 24 hours.

Although this alloy has excellent properties, one would expect it to have a shorter aging time, higher strength, and greater stability at high temperature. The inventors ultimately decided to add rhenium (Re) to the prior art, allowing approximately the following percentages by weight: Mo: 20-30%, Cr: 5-10%, Re: 3-10%, Ni: 60-70%. The rhenium was selected because it has a relatively large atomic diameter (0.27 nm), a high melting point (3459 K), and a high modulus of elasticity (329 GPa). The large atomic diameter and high melting point elements diffuse relatively slowly so that the kinetics of the precipitate growth will be sluggish and the alloy can be used for long periods without over-aging. The high modulus enhances the strength of the alloy. If the additional element can participate in the precipitation, the large atomic diameter also results in more distortion in the lattice of the matrix and accelerates the nucleation of the precipitates.

Our experimental results demonstrate that the addition of rhenium increases the Young's modulus and storage modulus by 10-20% and enhances the stability of the materials during aging. At the same time, the Re accelerates the LRO precipitation hardening by almost 36 times. FIG. 1 shows a plot of hardness versus the length of aging (note that the X-axis is logarithmic). The hardness of a sample annealed at 1473 K is about 200 HV (1 HV=1 Kg/mm²=9.8 MPa). Aging at 873 K for 1 minute increases hardness by 25%. In the selected area diffraction patterns, samples aged at 873 K for 1 minute show both the diffused SRO and LRO (A₂B type) diffraction spots. However, the intensity of the LRO reflections is much stronger than SRO, indicating that the volume fractions of the LRO domains are larger than the SRO ones.

FIG. 2 shows a comparison of age hardening of the new alloy versus age hardening of a prior art material which is typically subjected to age hardening (such as HAYNES 242, which is a well known Ni—Mo—Cr alloy). The reader will observe the dramatic reduction in aging time for the rhenium containing alloy.

For the new alloy, the A₂B type LRO domain sizes appear to be about 1-5 nm for materials aged at 873 K (600 degrees Celsius) for 1 minute. These domain sizes are about 5 crystallographic unit cell sizes when one views the sample in the −[001] orientation of the matrix. Therefore, the addition of rhenium reduces the age-hardening time by acceleration of the A₂B type LRO precipitate formations with initial size, r, of a few nanometers, where A is Ni and/or Re and B is Mo and/or Re. The beneficial effect of the rhenium addition could be explained by the location of the Re in the materials under the following possibilities: (i) Re accelerates the precipitation by formation of (Ni,Re)₂Mo; (ii) Re accelerates the formation of the Ni₂Mo precipitates which exist in its absence but Re will not occupy any sites in the precipitates; (iii) the Re, combining with Ni and Mo, forms nuclei of Ni₂(Mo,Re), where the addition of Re merely increases the supersaturation of the solute atoms for formation of the LRO precipitate of Ni₂(Mo,Re); (iv) the Re, combining with Ni and Mo, forms nuclei of Ni₂(Mo_(n)Re_(m)), where the addition of Re does not only increasing the supersaturation of the solute atoms for formation of the LRO precipitate but also occupy an ordered position in B sites of A₂B type precipitates; or (v) Re and Ni form ordered clusters acting as nucleation site for Ni₂(Mo, Re) nucleation's, i.e., Re forms nuclei of precipitates at an earlier stage than would occur in its absence. To elucidate the impact of Re, i.e., how the Re atoms accelerate the aging we closely examined the atomistic structures of the materials in Z-contrast images in combination with our calculations.

Our Z-contract imagines demonstrate that Re atoms occupy the site B in the A₂B precipitates. Therefore, its behavior is similar to Mo in the LRO domains and, (i) and (ii) can be excluded. Although Re atom occupies the Mo position in the ordered domains, the Z-contrast images show that Re atom forms no clusters in the Mo positions. Therefore, Re atoms act as neither a cluster nor ordered domains within the B sites in A₂B to form Ni₂(Mo_(n)Re_(m)) for acceleration of the nucleation of the LRO domains. Therefore, no evidence for explanation (iii) can be found in our experimental data. Close examinations of the HRTEM images demonstrate that the most of the SRO and LRO atoms are in the same locations, indicating that LRO occurs in the same location of the SRO. Thus, the Re additions link the SRO and LRO. Z-contrast image shows that the Re atoms, indicated by arrows, stay within the LRO domains close to Ni₂Mo type crystallographic structures. The isolated Re atoms act individually to combine with Ni atoms in acceleration the nucleation of the LRO domains. Therefore, the possible explanations are (iv) and (v) in the last paragraph. Calculations demonstrate that the formation energies for Ni₂Mo and Ni₂Re are −0.127 and −0.141 ev/atom, respectively, making the explanation in scenario (v) more plausible than the rest. This fact indicates that nucleation of Ni₂ Re reduces the system energy even at the early state of age hardening. It appears that the Re atoms act as a catalyst for early nucleation of the LRO domains by formation of Ni, Re and therefore accelerated the age hardening process. Thus, it appears that the Re atoms should occupy the Mo positions in the ordered domains in the final products observed by various microscopy technologies.

Further increasing the aging time from 1 to 4 minutes hardens the material by approximately an additional 25% (resulting from the perfection of the LRO). At this time the material almost reaches its maximum hardness without deformation. The domain sizes of the LRO grow up to 10 nm. Without the Re additions, the LRO domains homogenously nucleate from different locations from the SRO domains and therefore the LRO kinetic is sluggish. Consequently, the prior art alloy requires about 144 minutes to reach the hardness values achieved by the alloy with Re additions in about 4 minutes.

The short aging time of the new alloy indicates that the inventive precipitate-hardened alloy can be produced in an energy efficient manner compared with other alloys. The high strength, high modulus, and thermal stability demonstrate that the alloy can substitute various existing Ni-based alloys with superior properties.

After 4 minutes, the increase in hardness levels out. Thereafter, increasing the aging time to 4 hours at 873 K results in no significant change of the LRO domains compared with those formed when the aging time is only 4 minutes. Even after 529 hours of aging, the hardness shows no sign of decreasing (indicating that over-aging does not occur in this interval). The alloy produced using the present inventive process is thereby seen to be resistant to overaging.

Therefore, a minimum aging time of under 5 minutes and preferably close to 4 minutes is best in terms of energy efficiency. However, extended aging times of 15 minutes, 50 minutes, or longer can be used without fear of overaging. Some heat treaters will naturally elect to extend the aging time beyond 4 minutes in order to ensure that near-maximum hardness is achieved.

In practical applications, some users hope that the new alloys can also be processed by existing heat treatment protocol, such as long aging time. This can be achieved by deformation in the invented alloy. Cold work significantly changes the ordering kinetics and consequently the age-hardening behavior of the new nickel-based superalloy. FIG. 3 shows the hardness values of samples which were annealed at 1473 K (1200° C.) for 8 hours, then deformed to 41%, 62%, and 69%. Following the cold work, the samples were aged at 873 K (600° C.) from 36 minutes to over 529 hours. The reader will observe four distinct stages in the precipitation hardening process.

In the first stage (from roughly 36 minutes to 2.4 hours) little age-hardening was observed. Therefore, deformation increases the entropy of the system and makes the SRO partially disappear. In this incubation stage, the age-hardening process operates by nucleation of new LRO domains and requires a longer time in the deformed samples than annealed ones. In the second stage (roughly from 2.4 hours to 4 hours), the hardness values ramp up to 530 HV for 41%, 589 HV for 62%, and 609 HV for 69% deformation strains respectively. A high degree of LRO occurs in this stage. Therefore, the hardening behavior of the cold-worked samples is markedly different from that of the un-worked annealed ones. The hardening is delayed from 4 minutes to about 4 hours at the aging temperature of 873 K (600° C.). This is a remarkable result, as it demonstrates that for this type of alloy cold work decelerates the aging process by a factor of 60, and users can process the alloys as the prior art alloys.

The hardness increases shown in the plots are accompanied by comparable increases in strength, thanks to the presence of the LRO. The ultimate tensile strength and yield strength are respectively 1795 MPa and 1780 MPa for samples worked to 69% strain and then aged to 873 K (600° C.) for 4 hours. The ultimate tensile strength and yield strength for cold worked samples are 1641 MPa and 1500 MPa respectively.

In the third stage of aging, the hardness values reach plateaus when aging times are between 4 hours and 50 hours. In the final stage when samples were aged from 50 hours to 529 hours, samples show a continuing decrease in hardness with increasing time. When the aging time reaches 529 hours, the hardness decreases to levels approximating the levels before aging began. The LRO domains, which have the chemistry of Ni, (Mo, Re) are highly developed. The interfaces between precipitates and the matrix are very sharp. In comparison with samples aged at 873K (600° C.) for 4 hours, not only are the LRO reflections intensified but also the size of the precipitates increased. This relates to the over-aging of the materials. The over-aging is not seen in annealed samples aged up to 529 hours.

Thus, the reader will understand that the formulation of the rhenium containing alloy—with the possible addition of strain hardening—allows a greatly enhanced mechanical strength.

The preceding descriptions contain considerable detail regarding the inventive process. However, these descriptions are properly viewed as defining the preferred embodiments, rather than the scope of the entire invention itself. Thus, the scope of the invention should be fixed by the following claims rather than by the examples given. 

1. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging, comprising: a. providing a metal alloy containing nickel, molybdenum, chromium, and rhenium; b. wherein said rhenium comprises 3% to 10% of the total weight of said metal alloy; c. wherein nickel comprises the majority of said metal alloy by weight; d. annealing said metal alloy; and e. after said annealing step, age hardening said metal alloy for a time interval of less than fifty minutes.
 2. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 1, wherein said age hardening is conducted at a temperature of about 873 K.
 3. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 1, wherein said time interval used for said age hardening is less than five minutes.
 4. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 3, wherein said time interval used for said age hardening is less than five minutes.
 5. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 3, wherein said age hardening is conducted at a temperature of about 873 K.
 6. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 4, wherein said age hardening is conducted at a temperature of about 873 K.
 7. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging, comprising: a. providing a metal alloy containing nickel, molybdenum, chromium, and rhenium; b. wherein said rhenium comprises 3% to 10% of the total weight of said metal alloy; c. wherein said nickel comprises 60% to 70% of the total weight of said metal alloy; d. wherein said molybdenum comprises 20% to 30% of the total weight of said metal alloy; e. wherein said chromium comprises 5% to 10% of the total weight of said metal alloy; f. annealing said metal alloy; and g. after said annealing step, age hardening said metal alloy for a time interval of less than fifty minutes.
 8. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 7, wherein said age hardening is conducted at a temperature of about 873 K.
 9. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 7, wherein said time interval used for said age hardening is less than fifteen minutes.
 10. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 9, wherein said time interval used for said age hardening is less than five minutes.
 11. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 9, wherein said age hardening is conducted at a temperature of about 873 K.
 12. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 10, wherein said age hardening is conducted at a temperature of about 873 K.
 13. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging, comprising: a. providing a metal alloy containing nickel, molybdenum, chromium, and rhenium; b. wherein said rhenium comprises 3% to 10% of the total weight of said metal alloy; c. wherein said nickel comprises 60% to 70% of the total weight of said metal alloy; d. wherein said molybdenum comprises 20% to 30% of the total weight of said metal alloy; e. wherein said chromium comprises 5% to 10% of the total weight of said metal alloy; f. annealing said metal alloy at a temperature above 1200 K; and g. after said annealing step, age hardening said metal alloy for a time interval of less than fifty minutes at a temperature above 800 K.
 14. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 13, wherein said age hardening is conducted at a temperature of about 873 K.
 15. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 13, wherein said time interval used for said age hardening is less than five minutes.
 16. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 14, wherein said time interval used for said age hardening is less than five minutes.
 17. A method for achieving accelerated age hardening in a metal alloy while minimizing the risk of over-aging as recited in claim 15, wherein said age hardening is conducted at a temperature of about 873 K. 